Concentrated water suspension of nutrients

ABSTRACT

A concentrated aqueous solution for the enrichment of foodstuffs containing a water soluble ferrous salt,thiamine, niacinamide, riboflavin that has been treated so as to remain in suspension, and as an anti-oxidant a combination of L-cysteine hydrochloride and ascorbic or erythrobic acid. The riboflavin suspension is produced by adding concentrated hydrochloric acid to the riboflavin and then adding the mixture to the aqueous solution containing the other nutrients and a suspending agent which is either methylcellulose, gum tragacanth or sodium carboxymethylcellulose.

United States Patent Spangler et al.

[ 1 Sept. 5, 1972 [54] CONCENTRATED WATER SUSPENSION 0F NUTRIENTS [73]Assignee: Merck & Co., Inc. Rahyvay li i [22] Filed: Aug. 20, 1970 [21]Appl. No.: 65,702

[52] US. Cl. ..424/147, 99/11, 99/28, 99/54, 99/83, 99/90 R, 99/93,99/105,

[51] Int. Cl. ..A21d 2/22, A2ld 2/28, A231 1/30 Field of Search ..99/11,14, 28, 54, 63, 105, 99/83, 93, 86, 90, 150, 155, 140 R, DIG. 1;

[56] References Cited UNITED STATES PATENTS 2,939,820 6/1960 Gerber eta1 ..424/295 2,829,054 4/1958 Feinstone ..99/1 1 3,219,454 11/ 1965Howard et a1. ..99/28 2,822,317 2/ 1958 Gulesich et a1. ..424/1473,080,234 3/1963 Jarowski ..99/14 OTHER PUBLICATIONS Spanyar et al.,Stabilization of Vit. C In Foods, Chem. Abst. Vol. 64, pages 18302-18303, 1966 Stone, Science, 3- 17- 50, Vol. III p. 283

Furia, Handbook of Food Additives, 1968, pages 126- 129 Fujimura,Biochemistry of L-Ascorbic Acid, Chem. Abst. Vol. 46, pages 4587- 4588,1952 Primary Examiner-Morris O. Wolk Assistant ExaminerStephen B. DavisAttorney-Raymond Underwood, Harry E. Westlake, Jr. and 1. Louis WolkABSTRACT A concentrated aqueous solution for thev enrichment offoodstuffs containing a. water soluble ferrous salt,thiamine,niacinamide, riboflavin that has been treated so as to remain insuspension, and as an antioxidant a combination of L-cysteinehydrochloride and ascorbic or erythrobic acid. The riboflavin suspensionis produced by adding concentrated hydrochloric acid to theriboflavinand then adding the mixture to the aqueous solution containingthe other nutrients and a suspending agent which is eithermethylcellulose, gum tragacanth or sodium carboxymethylcellulose.

5 Claims, No Drawings CONCENTRATED WATER SUSPENSION OF NUTRIENTS RELATEDCASES Ser. No. 858,892; filed on Sept. 17, 1969 and now abandoned Ser.No. 30,978; filed on Apr. 22, 1970 and now abandoned Ser. No. 32,427;filed on Apr. 27, 1970 and now abandoned This invention relates to aconcentrated water suspension of nutrients and particularly to one thatcontains vitamins and an iron salt in the proper ratio for theenrichment or fortification of processed foods.

The invention is of special value to the bakery industry using flourbecause in refining wheat grains to make the popular white flour aconsiderable amount of the naturally contained nutrients is removed. Tocompensate for this, or, to supply other nutrients the flour has beenenriched by the addition of these nutrients directly to the flour.Generally, the nutrients are added into the doughs from which bakedproducts are to be made; usually they are vitamins.

Iron is an essential nutrient which may be seriously deficient in theaverage daily diet. It is an integral part of the structure andfunctions of several enzymes and of hemoglobin. The National Academy ofSciences re ported in its Publication No. 1694 on Recommended DietaryAllowances that it is impractical to supply in an otherwise adequatediet the iron needs of the population particularly women, infants, andchildren. They observe that "it is desirable to increase the ironcontent of the diet through fortification.

Vitamins and iron are critically absent from refined white flour butwhole wheat flour and other grain products such as those from corn,oats, barley and rye are low in these essential nutrients. Consequently,food scientists and nutritionists have sought ways to augment thevitamin and iron content of bakery products. Although vitamins and ironcan be added directly to the flour the baker normally purchasesunenriched flour and fortifies it himself directly in the bakingprocess.

To produce bakery products with the desired large amount of vitamins andiron the practice has been to add to the dough mix the necessary amountof each separate powdered nutrient in the form of blends, mixtures, ortablets, which contain the nutrients in the ratio desired. Occasionallythe nutrients are added separately.. None of these practices is entirelysatisfactory for several reasons. If the separate nutrients are added inpowdered form the danger is always present that all of them will not bemeasured out exactly. Some of the nutrients are added in very smallamounts, especially if the dough batch is small and an accuratemeasurement of such quantities is particularly time consuming.

Powdered blends or mixtures of nutrients may be nonuniform as to bulkdensity or ingredient content so that even distribution in the food tobe fortified may be difficult to achieve. Some of these nutrients differsufficiently in particle size, or shape, or specific gravity that theytend to segregate or lose their uniformity of distribution throughoutthe mass during shipping. The dust from these powdered blends ormixtures have been known to cause allergenic reaction when handled bycertain individuals.

When compounded in the form of tablets or wafers these complications ofhandling powdered nutrients are I present although to a lesser extent.In addition, since they are generally counted out, there is the everpresent risk that an operator may forget to use them or make an error incounting the proper number. Tablets are of little value in a systemrequiring a continuous uniform flow of ingredients unless they are firstdisintegrated and uniformly dispersed in water. An additional adversefactor is that the tabletting of the nutrients is costly.

The present invention involves the formation of an aqueous preparationof the nutrients ordinarily used to fortify bakery products or otherfoods. This especially involves the selection of a particular suspendingagent to prevent riboflavin from settling and it also involves theselection of the proper salt form of the other vitamins and the ironwhich are included.

As riboflavin is very water insoluble the invention involves thediscovery that it will stay in suspension if it is first combined withconcentrated HCl and then added to the water with certain suspendingagents present. The riboflavin cannot first be added to the water. To0.094 grams of riboflavin is added one and a half ml. of concentratedHCl but 60 percent more or less volume of the acid may be used. It isthen added to water with the other nutrients and as a suspending agenteither methylcellulose, gum tragacanth or sodium carboxymethylcelluloseis added.

If methylcellulose is used it should have about a 29 percent methoxylsubstitution and be used as a 100 cps viscosity water solution. The gumtragacanth is the dried gummy exudate commonly used in pharmaceuti-- caland food practices. If sodium carboxymethylcellulose is used it shouldhave about a 0.75 percent carboxymethyl substitution and a l,0002,800cps viscosity at 25 C. in a 1 percent water solution. One ofthem wouldbe added in the amount of 0.01 to 0.6 grams per m1. of the total finalpreparation.

As elemental iron is insoluble in water the invention involves the useof the water soluble ferrous salts such as ferrous sulfate. Thiaminehydrochloride or thiamine nitrate and niacin or its amide may be used inthese forms as they are sufficiently water soluble. Other water solublenutrients can be added and treated in similar fashions.

As the ferrous iron is rather readily oxidized to the ferric ion whichprecipitates from the system it is important that this oxidation beprevented. This is accomplished by employing a combination of L-cysteinehydrochloride and ascorbic or erythorbic acid as it is synergistic as anantioxidant in this system and neither one alone is fully effective forthis purpose. Equal weights of the L-cysteine HCl and the ascorbic acidor erythorbic acid are preferred but the invention may be practicedwithin a 124.7 to a 4.7:1 ratio by weight. Together, they should add upto 3 to 7.5 grams per 100 m1. of the solution and 5 grams is preferred.The water soluble salts, such as sodium and potassium, of these acidsmay be used but in an increased amount so that the desired actual amountof the acid is present and this is included in the invention and claims.

The ferrous sulfate should amount to between 4 and 24 grams in 100 ml.of the solution. An equivalent weight of another water soluble ferroussalt can be used so that the same amount of the ferrous ion is present.The riboflavin HCl-premix should amount to 0.03 to 0.11 grams per 100ml. of solution. The thiamine should amount to 0.05 to 0.7 grams per 100ml. of solution. The niacinamide should amount to 0.5 to 3.0 gms. per100 ml. of solution.

The invention contemplates the addition of other water soluble vitaminsto the water, such as cyanocobalamin and pyridoxine hydrochloride.Another reducing agent may also be added to further assure the stabilityof the system. Other water soluble agents such as flavors, doughconditioners, yeast food, water conditioners or coloring materials maybe added to the water so that the solution serves as a carrier tointroduce them in the bakery product.

It is highly important that the water be free of dissolved atmosphericoxygen but this is not absolutely essential as its presence may beoffset by adding the antioxidants at the higher limits of the statedrange. ,To remove the atmospheric oxygen the water may be boiled, orplaced under a high vacuum or sparged with nitrogen.

The nutrient solution described in the invention has many advantages. Ifit is visible, as in a glass tank or it flows through a transparentconduit it has an attractive appearance. It does not create a dustproblem. It is economical in contrast to the cost of making compressedtablets. It can be stored in elevated tanks so that floor or table spaceis not occupied. The tanks will ordinarily be at such a high positionthat the solution will flow by gravity directly to the use location,thus eliminating pumps, scoops or weighing apparatus. When desirable,the solution flow rate is readily controlled by a variety of liquidmetering devices.

An exceptional benefit of the invention is its ease of handling as theworker may remain at the use location and merely turn a valve which isreadily at hand. This makes it possible to more accurately add thestipulated amount, as a metering device in the line can be watched untilit is time to stop the flow. Of course, an automatic volume controlledshut-off mechanism may be used. As the solution is a uniform onethroughout, it is assured that all equal volumes from first to last willcontain an equal amount of the nutrients.

Representative examples of the invention are the following. Theexpression, riboflavin-l-lCl represents a premix of concentrated HClacid and riboflavin as described above.

EXAMPLE 1 Riboflavin-HCI 0.07 gms. Thiamine Hydrochloride 0.19 gms.Niacin amide 1.20 gms. Ferrous Sulfate 22.50 gms. L-CysteineHydrochloride 3.75 gms. Ascorbic Acid 3.75 gms. Methylcellulose, 29%methoxyl content,

100 cps water solution 0.05 gms.

Water q.s. to 100 ml.

The niacin amide is first dissolved in less water than the final total,during stirring. Then the methylcellulose is added and then theriboflavin-HCl premix. With continued stirring, the thiamine, ferroussulfate and cysteine HC1 are added in order. The preparation wasinitially observed to be transparent but slightly cloudy and it remainedthis way for 30 days. It was also stable with respect to assay of theactive ingredients at the end of that time.

EXAMPLE 2 Riboflavin-RC] 0.09 gms. Thiamine Hydrochloride 0.l9 gms.Niacin amide 0. l 2 gms. Ferrous Sulfate 22.50 gms. L-CysteineHydrochloride L25 gms. Ascorbic Acid 2.50 gms. Gum tragacanth 0.05 gms.

Water q.s. to ml.

It remained equally stable and transparent.

EXAMPLE 3 Example 1 was carried out but for the methylcellulose wassubstituted 0.025 gms. of sodium carboxymethylcellulose, having 0.75percent carboxymethyl substitution and a l,000-2,8000 cps. viscosity at25 C. in a 1 percent water solution. The same observation as totransparency and stability were made.

EXAMPLE 4 Riboflavin-HCI 0.ll gms. Thiamine Hydrochloride 0.60 gms.Niacin amide 0.80 gms. Ferrous Sulfate 15.00 gms. L-CysteineHydrochloride 2.50 gms. Ascorbic Acid L25 gms. Tragacanth 0.05 gms.Water q.s. to I00 ml.

The same observations as to transparency and stability were made.

EXAMPLE 5 Riboflavin-HCI 0.50 gms. Thiamine Hydrochloride 0.06 gms.Niacin amide 2.50 gms. Ferrous Sulfate 8.00 gms. L-CysteineHydrochloride 2.50 gms. Ascorbic Acid 2.50 gms. Tragacanth 0.05 gms.Water q.s. to 100 ml.

The same observations as to transparency and stability were made.

In using the solution of this invention about ml. of it is added to 100pounds of flour to produce 150 1- pound loaves of bread. Or moregenerally considered, 100 ml. of the solution would be added to make 1001- pound loaves of bread as this averages l m]. of solution per onepound of bread.

While the invention has been disclosed with special reference to the useof the concentrate to enrich bakery products, the concentrate may beused whenever or wherever fortifications of food products is desired.For instance, it may be added to canned vegetables, fruits and/orbeverages in the amount necessary so that an average serving will supplythe total amount or some portionof the daily nutrient requirements.Another use is to add the concentrate to the coating mixture which is tobe applied to cereals and biscuits.

In making the concentrated solution of the invention it may sometimes bethought desirable to have only the ferrous salt and ascorbic acid orerythorbic acid present. The invention contemplates this and in any ofthe above the examples one or all of the other vitamins, i.e. thiamineand niacinamide may be completely Water soluble ferrous salt omittedfrom the examples. Niacin may be substituted for niacinamide in theexamples. Instead of ferrous sulfate, it may be convenient to use thefumarate, citrate, lactate and other water soluble salts, or theirhydrates may be used, and these are to be considered as substitutes inthe examples. The sodium and potassium salts of ascorbic or erythorbicacid may be used instead of the acid.

These several equivalents of the agents stated in the examples are to beconsidered as being included in the appended claims.

What is claimed:

1. A concentrated aqueous preparation for the enrichment of food stuffswhich contains the following per 100 ml. of the preparation:

L-cysteine hydrochloride and an acid selected from the group consistingof ascorbic and erythorbic acids in a l:4.7 to 4.7:] ratio by weight,

totalling 3-7.5 gm.

Riboflavin-HG! premix of 0.094 g. at

riboflavin and L5 ml. 2 of cone. HCI

Thiamine Niacinamide Solubilizing agent selected form the groupconsisting of gum tragacanth, methylcellulose of 29% methoxylsubstitution and as a N0 cps viscosity water solution, and sodiumcarboxymethylcellulose of a 0.75% carboxymethyl substitution and aWOO-2800 cps. viscosity at 25 C. in a l% water solution 0.0! to 0.6 gm.

2. The concentrate of claim 1 in which the L-cysteine hydrochloride andthe selected acid add up to 5 grams.

3. The concentrate of claim I in which the riboflavin- HCl premix is amixture of 0.094 g. of riboflavin and 1.5 ml. concentrate HCl.

4. The concentrate of claim 1 in which thiamine hydrochloride orthiamine mononitrate is used.

5. The concentrate of claim 1 in which niacin is used.

2. The concentrate of claim 1 in which the L-cysteine hydrochloride andthe selected acid add up to 5 grams.
 3. The concentrate of claim 1 inwhich the riboflavin-HCl premix is a mixture of 0.094 g. of riboflavinand 1.5 ml. concentrate HCl.
 4. The concentrate of claim 1 in whichthiamine hydrochloride or thiamine mononitrate is used.
 5. Theconcentrate of claim 1 in which niacin is used.